Process for simultaneous cracking of lighter and heavier hydrocarbon feed and system for the same

ABSTRACT

The invention provides for a process and apparatus for simultaneous conversion of lighter and heavier hydrocarbon feedstocks into improved yields of light olefins in the range of C2 to C4, liquid aromatics in the range C6 to C8 mainly benzene, toluene, xylene and ethyl benzene and other useful products employing at least two different reactors operated in series with respect to catalyst flow and parallel with respect to feed flow under different regimes and process conditions with same catalyst system.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.13/638,460, which is the U.S. national stage of InternationalApplication No. PCT/IN2011/000223, filed Mar. 30, 2011, which claimspriority to Indian Application No. 793/DEL/2010, filed Mar. 31, 2010.The foregoing applications are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to a process for simultaneous cracking oflighter and heavier hydrocarbon feedstocks. In this process the lightand heavy feeds are processed in two different reactors operated inseries with respect to catalyst flow and parallel with respect to feedflow to produce light olefins in the range of C2 to C4 and aromaticproducts in the range C6 to C8 mainly benzene, toluene, xylene and ethylbenzene and other useful products. The present invention also relates toan apparatus for simultaneous cracking of lighter and heavierhydrocarbon feeds.

BACKGROUND OF THE INVENTION AND PRIOR ART

Light olefins like ethylene, propylene and butylenes are considered asthe major building blocks for the production of various petrochemicals.These chemicals are widely used for the production of polyethylene,polypropylene, di-isobutylene, polyisobutylene etc. Conventional steamcracking process remains the major source of light olefins, mainlyethylene and propylene to the petrochemical industry. In the emergingscenario, the demand growth of propylene as petrochemical feedstock isexpected to be much higher than that of ethylene. Propylene is the majorbyproduct from the steam cracking process, which contributes about 70%of world's propylene demand. About 30% of world's propylene demand isfrom the conventional Fluid Catalytic Cracking (FCC) units. In recentyears, there is a significant gap between the demand and supply ofpropylene. Consequently, the industry is in the lookout for technologyfor augmenting production of light olefins. To bridge the gap betweenthe demand and supply of propylene, a new catalytic process is requiredfor production of propylene as the primary product.

Fluid Catalytic Cracking (FCC) process is well known since 1942. Thehistory and the evolution of FCC process at various generations aredetailed in the book “Fluid Catalytic Cracking Handbook” by RezaSadeghbeigi, Gulf publishing company, “Fluid Catalytic Cracking” byWilson, and various other literatures.

In general, cracking is defined as breaking down of hydrocarbons ofhigher molecular weight into lower molecular weight hydrocarbons. It canbe carried out thermally or catalytically. In fluid catalytic crackingprocess, the catalyst is a fluidizable fine particle in the size rangeof 5-150 microns. The steps involved in the conventional FCC process aredescribed below:

-   i. Hydrocarbon feedstock is preheated to a temperature range of    150-400° C. to enhance the atomization/vaporization of feed;-   ii. The preheated feed is mixed with the steam at particular ratio    and passed through a nozzle to disperse the feed into fine droplets    inside an up-flow riser;-   iii. The dispersed feed gets contacted with the hot regenerated    catalyst at the bottom of the riser, where the reactions are    initiated to take place along the remaining length of the riser;-   iv. The mixture of catalyst and products of catalytic cracking is    separated by a termination device; further, the entrained catalyst    is separated from the product vapor by cyclone separators and    transferred to the catalyst bed in the reactor stripper;-   v. The entrapped hydrocarbon components are removed from the    separated catalyst by stripping using steam;-   vi. The coke laden fluidizable catalyst, often referred as spent    catalyst, is transferred to a regenerator through spent catalyst    standpipe and spent catalyst slide valve;-   vii. The deposited coke in the catalyst is burnt in the regenerator    using air and the hot regenerated catalyst is transferred to riser    through regenerated catalyst standpipe and regenerated catalyst    slide valve for the next cycle of operation.

In this manner, FCC process is termed as a cyclic process where thereaction and regeneration takes place continuously in a riser (reactor)and regenerator respectively. A particular amount of fresh catalyst isadded to the circulating inventory in order to maintain the activity ofthe catalyst while keeping the inventory at constant level.

In the present scenario, as worldwide crudes are becoming heavier,processing of heavy crudes has become important, especially to increasethe profit margin. Because of this, it is preferable to maximize theintake of vacuum residue or atmospheric residue in feed to FCC/RFCCunit. However, increase in concentration of heavy ends in FCC unit feedwill have several deleterious effects in the known resid FCC units. Theassociated problems in processing heavy residue in the FCC units are asfollows:

-   i. Excessive coke with the residue produces large amount of excess    heat in the regenerator and therefore, the heat balance of the    reactor regenerator results in lower conversion.-   ii. Higher metal level on the resid leads to significant    deactivation of the catalyst and requires incremental catalyst    addition to keep the metal level on equilibrium catalyst within    acceptable range. Crackability of some of the residues, in    particular aromatic residues, are not quite good leading to lower    conversion.-   iii. Strippability of the heavier unconverted residue inside the    catalyst pores is not efficient resulting in higher regenerator    temperature and thereby lower conversion.

The excessive coke in the catalyst generates lot of heat while burningin the regenerator, which limits the catalyst circulation rate to theriser reactor zone, thereby reduces the overall conversion. In order tomitigate this problem catalyst coolers are used conventionally in theresid FCC units, which cools the catalyst indirectly using steam/wateras the coolant. These coolers are disclosed in the U.S. Pat. Nos.2,377,935, 2,38,6491, 2,662,050, 2,492,948, and 4,374,750.

U.S. Pat. No. 5,215,650 discloses the indirect cooling of the hotregenerated catalyst via shell and tube heat exchanger type reactorwhere cracking of light alkanes like ethane, propane and butane takesplace and then the cooled catalyst is transferred to the riser reactor.U.S. Pat. No. 4,840,928 discloses the process of converting loweralkanes to olefins in a third bed, external catalyst cooler in which theexcess heat from the regenerator is used directly for thermal crackingof lower alkanes mainly propane with a WHSV of not exceeding 5 hf¹ inthe said reactor.

Production of light olefins from feed stocks like VGO is disclosed inthe U.S. Pat. No. 6,656,346, U.S. Pat. No. 4,980,053, U.S. Pat. No.6,210,562, U.S. Pat. No. 5,846,402, U.S. Pat. No. 6,538,169, U.S. Pat.No. 5,326,465, and US2006/0108260.

Production of light olefins from naphtha range feed stocks are disclosedin several documents like U.S. Pat. No. 4,287,048, U.S. Pat. No.5,232,580, U.S. Pat. No. 5,549,813, U.S. Pat. No. 6,288,298, U.S. Pat.No. 3,082,165, U.S. Pat. No. 3,776,838, U.S. Pat. No. 5,160,424, U.S.Pat. No. 5,318,689, U.S. Pat. No. 5,637,207, U.S. Pat. No. 5,846,403,U.S. Pat. No. 6,113,776, U.S. Pat. No. 6,455,750, U.S. Pat. No.6,602,403, U.S. Pat. No. 6,867,341, U.S. Pat. No. 7,087,155,US2001/042700, US2002/003103, US2003/220530, US2005/070422,US2006/10826, WO2000/18853, WO2002/26628, WO2004/078881, WO2006/098712.Catalytic Cracking of lighter feedstocks like propane, straight runnaphtha, olefinic naphtha to produce significant yields of light olefinshas its own limitation for commercial realization due to its less cokewhich affects the heat balance of the unit i.e. the ‘coke producedduring the reaction is not sufficient to produce the enough heat whichis required for cracking of lighter feeds.

U.S. Pate. No. 7,611,622B2 discloses a dual riser Fluid catalyticcracking (FCC) process with common regenerator involves cracking offirst hydrocarbon feed in first riser and cracking of second hydrocarbonfeed comprising light hydrocarbons including C3 and/or C4 hydrocarbons,in second riser to form second effluent enriched in light olefins andaromatics. Moreover this invention uses gallium included catalyst topromote aromatics formation.

Chinese patent CN 101522866A discloses a dual riser FCC process, whereinfirst and second hydrocarbon feeds (first hydrocarbon is olefin and thesecond hydrocarbon feed is paraffinic) are supplied to the respectivefirst and second risers to make an effluent rich in ethylene, propyleneand/or aromatics and the respective risers can have different conditionsto favor conversion to ethylene and/or propylene.

Some patent literatures, like U.S. Pat. No. 6,113,776, US2002/0003103,U.S. Pat. No. 7,128,827 disclose the concept of dual riser or multipleriser cracking where the portion of the catalyst is used for crackingthe lighter hydrocarbons like naphtha range feed stocks and the otherportion of catalyst is used in the conventional FCC riser. U.S. Pat. No.5,846,403 discloses the process in which the naphtha is injected in thesame reaction zone but at different elevations of the riser reactor.

None of the cited patents mention about the simultaneous Catalyticcracking of lighter feed stocks and heavier feed stocks in differentreactors operating in different regimes and conditions to producesignificant amount of light olefins and aromatics like benzene toluene,xylene, ethyl benzene etc.

An aim of the present invention is to provide a new catalytic crackingprocess for simultaneously cracking lighter and heavier hydrocarbonfeedstock to produce light olefins and liquid aromatic products.

Another aim is to provide a multiple reaction zone system that enablesthe production of light olefins and liquid aromatic products both fromlighter and heavier hydrocarbon cracking.

Yet another aim of the invention is to provide a catalyst system thatcan crack both lighter and heavier hydrocarbon under wide range ofoperating conditions.

A further aim of the present invention is to reduce the sulfur contentof the cracked products boiling in the range of C5 to 150° C. from firstreaction zone by not less than 60 wt%.

Another aim of the invention is to utilize the excess heat generated inthe regenerator due to excess coke burning, which in turn is due toprocessing of heavier feedstocks in the second reaction zone,effectively in the first reaction zone for cracking of lighterhydrocarbon feedstocks, thereby reducing the temperature of the catalystentering into the second reaction zone.

Another aim of the invention is to provide a suitable apparatus forcarrying out the said new catalytic process.

SUMMARY OF THE INVENTION

The present invention discloses a catalytic cracking process in whichlighter hydrocarbon feed stocks like propane, butane, isobutane,n-butenes, isobutene, straight run naphtha, visbreaker naphtha, cokernaphtha, FCC naphtha, hydrocracker and hydrotreater naphthas, naturalgas condensate, LPG condensate, gas well condensate are processed in thefirst reaction zone utilizing the excess heat of regenerated catalystdue to processing of heavier feedstocks in the second reaction zoneusing single catalyst composition.

DESCRIPTION OF THE INVENTION

The present invention provides a process for simultaneous catalyticcracking of lighter and heavier hydrocarbon feedstocks into improvedyields of light olefins, liquid aromatics and other useful products inmultiple reaction zones in different reactors operating under differentregimes and conditions comprising the steps of:

-   a) cracking the lighter hydrocarbon feedstock in a first reaction    zone in the first reactor to get a first reactor effluent mixture;-   b) separating the first reactor effluent mixture of step (a) into a    vapor rich phase and a solid rich phase;-   c) separating the vapor rich phase of step (b) in a product    separator into C5− fractions as the light olefins product and C5+    fractions;-   d) recycling the C5+ fractions back to the first reaction zone and    continuing the cracking operation until the aromatics concentration    in C5+ fraction reaches more than 90 wt %;-   e) stripping a portion of the solid rich phase of step (b)    containing coke laden catalyst using steam to remove entrapped    hydrocarbons along with vapor rich phase entering the product    separator;-   f) transferring the remaining portion of the solid rich phase of    step (b) containing coke laden catalyst from the first reaction zone    to a second reaction zone of a second reactor, cracking the heavier    hydrocarbon feedstock therein at a relatively lesser temperature and    pressure as ‘compared with those in the first reaction zone to get a    second reactor effluent mixture;-   g) separating the effluent mixture of step (f) into a vapor rich    phase and a solid rich phase containing coke laden spent catalyst;-   h) fractionating the vapor rich phase of step (g) to get different    cracked products;-   i) stripping the solid rich phase of step (g) using steam to remove    entrapped hydrocarbons along with vapor rich phase of step (g);-   j) regenerating the coke laden stripped spent catalyst obtained from    step (i) and step (e) in a common catalyst regenerator using air    and/or an oxygen containing gas to produce an active regenerated    catalyst for recirculating to the first reaction zone through    regenerated catalyst standpipe and regenerated catalyst slide valve    for the next cycle of operation.

This invention also provides a multi-reactor fluidized bed catalyticcracking apparatus for the production of light olefins and liquidaromatics etc. through simultaneous cracking of lighter and heavierhydrocarbon feedstocks in separate reaction zones comprising at least afirst reaction zone in a first reactor (4), a second reaction zone in asecond reactor (6) and a catalyst regenerator (12).

According to the said process lighter hydrocarbon feed is cracked withsteam in a molar ratio in the range of 1:60 and 60:1 in a bubbling orturbulent bed first reaction zone with a hot regenerated catalystmixture operated in a temperature range of 500 to 750° C. and pressurein the range of 1 to 5 kg/cm² to obtain first reactor effluent mixturecomprising cracked hydrocarbon product vapor and a coke laden catalyst.The first reactor effluent mixture is separated into a vapor rich phaseand a solid rich phase containing the coke laden catalyst. The vaporrich phase is cooled and separated into C5− and C5+ fractions in aseparator and the C5+ fraction is recycled to the first reaction zoneuntil the aromatics concentration in C5+ product from the first reactionzone reaches more than 90 wt %. A portion of the solid rich phasecontaining coke laden catalyst is stripped using steam to removeentrapped hydrocarbons along with the vapor rich phase entering into theproduct separator. The remaining portion of hot coke laden spentcatalyst is transferred from first reaction zone to second reaction zonecomprising a riser operating in fast fluidization regime or pneumaticconveying regime, the heavier hydrocarbon feed stock is cracked in thesecond reaction zone operated in the temperature range of 450 to 700° C.and pressure in the range of 0.9 to 4.9 kg/cm² to obtain a secondreactor effluent. The second reactor effluent is separated into a vaporrich phase and a solid rich phase containing coke laden catalyst. Thevapor rich phase is removed and fractionated to get the crackedproducts. The solid rich phase is stripped from the second reaction zoneusing steam to remove entrapped hydrocarbons along with vapor rich phaseentering into the fractionating column for separation into products. Thecoke laden catalyst obtained from second stripping zone and the cokeladen catalyst obtained from first stripping zone are regenerated in acommon regenerator using air and/or oxygen containing gas to produce hotregenerated catalytic mixture.

An embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, furthercomprises transferring active hot regenerated catalytic mixture to thefirst reaction zone for the next cycle of operation.

Another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe lighter hydrocarbon feed comprises. C3 fraction containing propaneand propylene and C4 fraction containing n-butane, isobutane, isobutene,butene-1, cis-2-butene, trans-2-butene and hydrocarbons boiling upto220° C. (true boiling point basis).

An embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe lighter hydrocarbon feed is selected from petroleum based light feedstock, such as propane, butane, isobutene, n-butenes, isobutane,straight run naphtha, visbreaker naphtha, coker naphtha, FCC naphtha,hydrocracker naptha, hydrotreated naphtha, natural gas condensate, LPGcondensate and gas well condensate or mixtures thereof.

Yet another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe lighter hydrocarbon feed is preferably selected from straight runnaphtha, visbreaker naphtha, coker naphtha, FCC naphtha, Hydrocrackerand hydrotreater naphtha, natural gas condensate, LPG condensate, andGas well condensate or mixture thereof.

It is an embodiment of the present invention to provide a process,wherein the cracking operation in the first reaction zone is carried outat a temperature of 500-750° C., preferably at a temperature of 550-700°C., pressure of 1 to 5 Kg/cm² and WHSV of 1 to 200 hf′ preferably at aWHSV of 6 to 120 hf′, whereas the said operation is carried out in thesecond reaction zone at a temperature of 450-700° C., preferably at480-600° C., pressure of 0.9 to 4.9 Kg/cm² and WHSV of 10 to 400 V¹,preferably at 60-250 hf′.

Further embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe heavier hydrocarbon feed has an initial boiling point of more than220° C.

Another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe heavier hydrocarbon feed is selected from petroleum based heavy feedstock, such as vacuum gas oil (VGO), visbreaker/coker heavy gas oil,fuel oil, coker fuel oil, hydrocracker bottoms, vacuum slop, cycle oils,foots oil, slurry oils, atmospheric gas oil, atmospheric residue andvacuum residue or mixtures thereof.

Still another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe Conradson carbon residue of the heavier hydrocarbon feeds is in therange of 0.1-15 wt %.

Yet another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe Conradson carbon residue of the heavier hydrocarbon feeds is morethan 3 wt %.

Hydrocarbon feed for the present invention comprises hydrocarbonfractions starting from carbon number 3 to carbon number 100 and above.The lighter hydrocarbon fraction could be propane, butane, isobutane,n-butenes, isobutene, straight run naphtha, visbreaker naphtha, cokernaphtha etc. and the heavier hydrocarbon fraction could be straight run,light and heavy vacuum gas oil, hydrocracker bottom, heavy gas oilfractions from hydrocracking, FCC, visbreaking or delayed coking,atmospheric residue, vacuum residue, vacuum slops etc. The conditions inthe process of the present invention are adjusted depending on the typeof the feedstock so as to maximize the yield of light olefins and liquidaromatic products like benzene, toluene, xylene, ethyl benzene etc. Theabove feedstock types are for illustration only and the invention is notlimited in any manner to only these feedstocks.

Further embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe catalyst is made up of solid micro-spherical acidic materials withaverage particle size of 60-80 micron and apparent bulk density of0.7-1.0 gm/cc.

Another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe catalyst is specifically designed to handle both the lighter andheavier feed stocks in first and second reaction zones respectively toselectively produce light olefins like ethylene, propylene and aromaticliquid products like benzene, toluene, xylene, ethyl benzene etc.

The catalyst employed in the process of the present invention is havingunique composition which comprises Y-zeolite in rare earthultra-stabilized form, bottom cracking components consists of peptizedalumina, acidic silica alumina or gamma-alumina, pentasil shapeselective zeolites or a mixture thereof. It may be noted that both thefirst and second stage reaction zone are charged with the same catalystand its composition is designed in such a way that it can optimallycrack both the lighter and heavier hydrocarbon feed. It may also benoted that conventional FCC catalyst mainly consists of Y-zeolite indifferent forms as active ingredient to accomplish catalytic crackingreactions.

In the process of the present invention, the active catalyst componentsare supported on relatively inactive materials such as silica/alumina orsilica-alumina compounds, including kaolinites or with active matrixcomponents like pseudobomite alumina. The active components could bemixed together before spray drying or separately binded, supported andspray-dried using conventional spray drying technique. The spray-driedmicro-spheres are washed, rare earth exchanged and flash dried toproduce finished catalyst particles. The finished micro-sphereScontaining active materials in separate particles are physically blendedin the desired composition.

Still another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe lighter hydrocarbon and steam at saturated or at superheatedconditions are mixed in the zone prior to the contact with the catalystand uniformly distributed using any of the conventional distributorslike manifold type, concentric ring type, perforated plate type, etc.into the first reaction zone.

Further embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe lighter hydrocarbon feed and steam at saturated or at superheatedconditions are uniformly contacted with hot catalyst from the commonregenerator in the first reaction zone.

Another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe ethylene to propylene ratio in the first reaction zone can be variedby tuning the steam to hydrocarbon feed mole ratio in the range of 1:60and 60:1 along with changes in the process variables.

Yet another embodiment of the present invention provide a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe coke on the catalyst from the first reaction zone is not more than0.35 wt %.

Further embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe regenerator can be a single stage or multistage to burn the entirecoke laden spent catalyst to form regenerated catalyst with coke contentnot exceeding 0.09 wt %.

Another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe sum of yields of ethylene plus propylene is not less than 25 wt % inthe first reaction zone and not less than 15 wt % in the second reactionzone.

Another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe excess heat generated in the regenerator due to processing of heavyfeedstocks in the second reaction zone is utilized effectively forcracking the lighter hydrocarbon feedstock at very high temperatures inthe first reaction zone.

Still another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe common regenerator can be a single stage or multistage to burn theentire coke laden spent catalyst to form regenerated catalyst with cokecontent not exceeding 0.09 wt % and thus meeting the heat requirement ofthe first and second reaction zones.

Another embodiment of the present invention is to provide a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinthe light and the heavy feeds are processed in two different reactorsoperated in series with respect to catalyst flow and parallel withrespect to feed flow to produce light olefins in the range of C2 to C4and aromatic products in the range C6 to C8 mainly benzene, toluene,xylene and ethylbenzene.

Another embodiment of the present invention provides a process forsimultaneous cracking of lighter and heavier hydrocarbon feeds, whereinC5+ fraction of the products from first reaction zone is recycled to thefirst reaction zone and the cracking operation is continued until thearomatics concentration in C5+ fraction reaches more than 90 wt %.

Yet another embodiment of the present invention is to provide a processfor simultaneous cracking of lighter and heavier hydrocarbon feeds,wherein the liquid product boiling in the range of C5 to 220° C. fromboth first and second reaction zones rare separated to produce variouspetrochemical feedstocks primarily benzene, toluene, xylene andethylbenzenec.

Further embodiment of the present invention is to provide acatalytically cracked product, wherein the propylene to ethylene ratioin the products from second reaction zone is not less than 2.5:1.

The conversion in the second reaction zone defined as sum of allproducts boiling less than or equal to 220° C. plus coke is not lessthan 70 wt %.

Yet another embodiment of the present invention is to provide a processfor cracking lighter and heavier hydrocarbon feedstock simultaneously,wherein there is a multiple reaction zone system that enables theproduction of light olefins and liquid aromatic products both fromlighter and heavier hydrocarbon cracking.

An embodiment of the present invention is to provide a catalyst systemthat can crack both lighter and heavier hydrocarbon under wide range ofoperating conditions.

Further embodiment of the present invention is to reduce the sulfurcontent of the cracked products boiling in the range of C5 to 150° C.from first reaction zone by not less than 60 wt%.

Another embodiment of the present invention is to utilize the excessheat generated in the regenerator due to burning of excess coke producedby the cracking of heavier feedstocks in the second reaction zone,effectively in the first reaction zone for cracking of lighterhydrocarbon feedstocks thereby reducing the temperature of the catalystentering into the second reaction zone.

The main products in the process of the present invention are the lightolefins and liquid aromatic products in the range C6 to C8 mainlybenzene, toluene and xylene. Light olefins include ethylene, propylene,isobutylene, trans-2-butene, cis-2-butene, butene-1 etc. Other usefulproducts of the present invention comprise LPG (C3 and C4), Gasoline(C5-150° C.), Heavy naphtha (150° C.-216° C.), Light Cycle oil (216-370°C.) and Bottoms (370° C.+).

DETAILED DESCRIPTION OF THE INVENTION

FIG. 1 shows a fluidized bed cracking apparatus with multiple reactionzones according to the present invention.

Fluidized catalytic cracking (FCC) process of the present invention toproduce light olefins and aromatics rich liquid products etc. throughsimultaneous cracking of light and heavy feeds in separate reactionzones utilizes at least two reactors. Fresh heavy feed (1) is injectedat the bottom of the riser through a single or multiple feed nozzle (2), wherein the heavy feed is mixed with the dispersion steam (3) so asto enable the better atomization of the feed molecules in the riser. Thehot partially coked catalyst from the first reactor 4) enters into thebottom of the riser (6) through the slide valve (5) whereupon it comesinto contact with the atomized feed. The catalyst along with hydrocarbonfeed and product vapors ascend the riser, wherein the recycle slurry (7)gets in to contact with the catalyst for re-cracking. The entire mixtureof catalyst, products and unconverted feed ascend the riser and at theend of the riser coked spent catalyst is separated from the hydrocarbonvapor in the riser termination device (8). The hydrocarbon vaporsleaving from the riser reactor are sent to a main fractionator columnvia plenum chamber (9) for separating into the desired products. Thecoked catalyst is subjected to steam stripping in a stripper (10) toremove the entrapped hydrocarbons from the catalyst. The strippedcatalyst is passed to a regenerator (12) through a slide valve (11) anddistributed via

spent catalyst distributor (13) where the coke deposited on the catalystis burnt off by means of air or any oxygen containing gas which isdistributed through the air distributor (14).

The clean hot catalyst from the regenerator passes through the slidevalve (15) and distributed in the fluidized dense bed reactor (4)through the regenerated catalyst distributor (16). Preheated fresh lightfeed (17) and recycled light feed (18) are mixed with the process steam(19) at the bottom of the conduit (20) and distributed in the light feeddistributor (21) where upon it gets contacted with the clean hotregenerated catalyst. The cracked products along with entrained catalystis separated in the separation device (22) wherein the product ofcracking is separated from the entrained catalyst and sent to thefractionation column to separate into various products. The partiallycoked catalyst from reactor (4) is circulated back to the bottom of theriser through the slide valve (5).

The invention and its embodiments are described in further detailshereunder with reference to the following examples which should not beconstrued to limit the scope of the invention in any manner. Variousmodifications of the invention that may be apparent to those skilled inthe art are deemed to be included within the scope of the presentinvention.

EXAMPLE 1

Yield of Light Olefins at Different Conversions in Conventional FCCOperation This example illustrates the change in yield of the lightolefins at different conversion levels under conventional FCCconditions. 216° C. conversion is defined as the total quantity ofproducts boiling below 216° C. including coke. The experiments wereconducted in standard fixed bed Micro Activity Test (MAT) reactordescribed as per ASTM D-3907 with minor modifications indicatedsubsequently as modified MAT. The catalyst is steamed at 810° C. for 3hours in presence of 100% steam prior to conducting the experiments. Theproperties of Feed-A used in the modified MAT reactor are given in theTable-1.

TABLE 1 Properties of Feed-A Unit Feed-A Property Density @ 15° C. gm/cc0.9116 Sulfur wt % 1.37 CCR wt % 0.17 Basic Nitrogen ppmw 489 Saturates(Paraffin + naphthene) wt % 62.6 Aromatics wt % 37.4 Distillation, ASTMD-1160  5 vol % ° C. 395 10 vol % ° C. 410 30 vol % ° C. 445 50 vol % °C. 470 70 vol % ° C.′ 495 90 vol % ° C. 545 95 vol % ° C. 570

The runs were, taken at a reaction temperature of 511° C., feedinjection time of 30 seconds with different severities by varying feedrate with the same catalyst loading. Catalysts used in this examplecatalyst A which is a commercially available FCC catalyst havingphysicochemical characteristics as shown in the Table below.

CAT-A Activity wt % 63.9 Al₂0₃ wt % 40.42 Re₂O₃ wt % 2.63 SA_(m)Z_(igni) 145 PV cc/gm 0.293 ABD gm/cc 0.89 APS micron. 103Crystalinity % 9.1 UCS °A 24.30

In all the examples, Dry gas is defined as the product comprising C 1and C2 hydrocarbons, and hydrogen, while LPG is defined as the productcomprising C3 and C4 hydrocarbons.

TABLE 2 Effect of severity on product yields Reaction Severity, W/F, min0.69 0.86 1.07 1.46 Yields, wt % Hydrogen 0.05 0.06 0.06 0.10 Ethylene0.64 0.90 0.97 1.14 Dry gas 1.13 1.39 1.73 2.19 Propylene 2.79 3.47 3.984.55 But-l-ene 0.83 0.99 1.08 1.19 Isobutene 1.26 1.37 1.42 1.39 trans-2Butene 1.31 1.54 1.63 1.73 Cis-2-Butene 0.80 0.94 1.00 1.06 LPG 7.359.13 11.00 13.09 Gasoline (C5-150° C.) 24.01 28.36 31.42 35.40 Hy.Naphtha (150-216° C.) 13.01 14.04 14.80 14.96 LCO (216-370° C.) 25.6825.23 24.20 21.93 216 Conversion, wt % 46.62 54.35 60.84 68.28

The product yields along with conversions are given in Table-2 whereinit is observed that with increase in severity conversions increasesalong with the increase in ethylene and propylene yields.

EXAMPLE 2 Yields of Light Olefins and Aromatics from Naphtha Cracking inConventional FCC Operation

This example illustrates the yield of the light olefins at conventionalFCC naphtha cracking operation. Cracking experiments are carried out at500° C. at the catalyst to oil ratio of 5.11. properties of the Feed-Bused in the modified MAT reactor are given in the following Table-3.

TABLE 3 Properties of Feed-B Property Unit Feed-B Density @ 15° C. gm/cc0.7358 Sulfur PPM 18 Paraffin wt % 39.6 Olefin wt % Nil Naphthene wt %47.7 Aromatics wt % 12.7 Benzene 0.83 Toluene 3.1 Xylene 4.25Distillation D-86  5 vol % ° C. 68.5 10 vol % ° C. 73.5 30 vol % ° C. 8850 vol % _° C. 100.8 70 vol % ° C. 113 90 vol % ° C. 132 95 vol % ° C.146.5

The light olefins yield is shown in the Table-4.

TABLE 4 Light olefins yield at 500° C. Reaction Severity, cat/oil 5.11Yields, wt % Ethylene 2.21 Propylene 4.72 But-l-ene 0.46 Isobutene 1.23trans-2 Butene 0.75 Cis-2-Butene 0.61

EXAMPLE 3 Effect of Recycle of Cracked Naphtha

This example illustrates the effect of recycle of cracked naphtha onliquid aromatics yield. The product obtained from Example-2 is recycledback i.e. cracked at similar conditions as mentioned in Example-2. Theyields of different aromatic products are shown in Table-5. This clearlyindicates that there is a significant increase in aromatics yield in 2ndrecycle product as compared to the first recycle product.

TABLE 5 Total aromatics content, % wt/wt 2nd Recycle Component 1stRecycle FCC product FCC product Benzene 3.8 5.3 Toluene 15.4 24.8 Ethylebenzene 1.6 2.3 m-p Xylene 10 15.6 o-xylene 2.8 4.8 n Propyl bebzene +methyl 1.4 0.3 ethyl benzene Tri methyl benzene + methyl 0.5 0.6 butylcyclopentane Tri methyl benzene + methyl 1.4 2.9 propyl cyclohexane

EXAMPLE 4 Yields of Light Olefins in the First Reaction Zone Using LightFeed

This example illustrates the yield of light olefins and other usefulproducts obtained in the first reaction zone of the present invention.The properties of feed used, the operating conditions maintained in themicro-reactor and the product yields are given in the Table-6

TABLE 6 Feed B Feed C Feed properties Density, g/cc @ 15° C. 0.73580.7223 Sulfur content, PPM 18 1600 IBP, ° C. 51 45 FBP, ° C. 153 160Operating conditions Reaction severity, W/F min 1.94 3.41 Reactiontemperature, ° C. 625 650 Yield, wt % Dry Gas 13.62 25.44 Ethylene 8.1714.76 LPG 39.48 37.75 Propylene 14.23 19.63 Gasoline (C5-150° C.) 38.6330.42 Heavy naphtha (150-216° C.) 3.87 3.97 LCO (216-370° C.) 2.06 0 CLO(370° C.+) 0 0 Coke 2.34 2.42

EXAMPLE 5 Yields of Light Olefins in Second Reaction Zone Using HeavyFeed

This example illustrates the yield of light olefins and other usefulproducts obtained in the second reaction zone of the present invention.The properties of feed used, the operating conditions maintained in themicro-reactor and the product yields are given in the Table-7

TABLE 7 Feed D Feed E Feed properties Density, g/cc @ 15° C. 0.89380.845 CCR, wt % 0.3 0.013 IBP, ° C. 330 339 FBP, ° C. 560 523 Operatingconditions Reaction severity, W/F min 1.068 1.098 Reaction temperature,° C. 580 580 Yield, wt % Dry Gas 10.53 4.4 Ethylene 6.74 2.66 LPG 49.3161.41 Propylene 23.65 25.9 Gasoline (C5-150° C.) 15.09 14.6 Heavynaphtha (150-216° C.) 5.31 3.54 LCO (216-370° C.) 9.12 6.18 CLO (370°C.+) 4.22 3.7 Coke 6.42 6.17 Conversion 216° C. 86.66 90.12

EXAMPLE 6 Effect of Temperature in the First Reaction Zone

This example illustrates the effect of temperature on yield of lightolefins and other useful products obtained in the first reaction zone ofthe present invention. The properties of feed used, operating conditionsmaintained in the micro-reactor and the product yields are given in theTable-8

TABLE 8 Feed F Feed F Feed properties Density, g/cc @ 15° C. 0.69520.6952 IBP, ° C. 52.8 52.8 FBP, ° C. 179.8 179.8 Operating conditionsWHSV, hr−1 24.43 22.64 Reaction temperature, ° C. 660 700 Productyields, wt % Dry Gas 26.57 39.45 Ethylene 14.21 23.67 LPG 37.2 30.56Propylene 20.92 18.72 Gasoline (C5-150° C.) 28.97 18.94

It is evident that by increasing the temperature in the first reactionzone, the yields of both ethylene and propylene increases significantly.

EXAMPLE 7 Effect of Weighted Hour Space Velocity (WHSV) in FirstReaction Zone

This example illustrates the effect of WHSV on yield of light olefinsand other useful products obtained in the first reaction zone of thepresent invention using the same feed (Feed-F) as that of Example-6. Theoperating conditions maintained in the micro-reactor and the productyields are given in the Table-9

TABLE 9 Operating conditions WHSV, hr−1 19.01 26.95 40.32 Reactiontemperature, ° C. 660 660 660 Product yields, wt % Dry Gas 27.71 26.6524.35 Ethylene 13.11 12.26 11.51 LPG 38.54 37.01 35.35 Propylene 23.3922.45 21.28 Gasoline (C5-150° C.) 25.4 27.98 30.35

It is clear that by increasing the WHSV in the first reaction zone, theyields of both ethylene and propylene decreases. From Example-6 & 7, itis clear that the process conditions as well as the hydrodynamic regimeis important in maximizing the yields of light olefins.

EXAMPLE 8 Combined Cracking of Light and Heavy Feed in Conventional FCCOperation Using Single Reaction Zone

This example illustrates the yield of light olefins and other usefulproducts obtained in the single reaction zone of the conventional FCCoperation. The feed to the reactor comprises 15 wt % light feed mixedwith 85 wt % of heavy feed. The combined feed properties, operatingconditions maintained in the micro-reactor and the product yields aregiven in the Table-10

TABLE 10 Feed G Feed properties Density, g/cc @ 15° C. 0.8574 CCR 2.17Sulfur, PPM 8500 Operating conditions Reaction temperature, ° C. 540Product yields, wt % Dry Gas 4.8 Ethylene 2.0 LPG 35.6 Propylene 12.5Gasoline (C5-180° C.) 40.4 LCO 12.1 CLO 2.4

EXAMPLE 9 Effect of Simultaneous Cracking of Light and Heavy Feed atDifferent Reaction Zone Operating at Different Conditions as PresentInvention

This example illustrates the yield of light olefins and other usefulproducts obtained in the first and second reaction zone of the presentinvention. Light feed corresponding to 15 wt % of total feed ofExample-8 is cracked in the first reaction zone at 680° C. and the heavyfeed corresponding to 85 wt % of total feed of Example-8 is crackedsimultaneously in the second reaction zone. The feed properties and theoperating conditions maintained in the micro-reactor for first andsecond reaction zone along with product yields are given in theTable-11.

TABLE 11 Reaction zone First Second Feed H Feed I (Light feed) (Heavyfeed) Feed properties Density, g/cc @ 15° C. 0.6798 0.8988 CCR — 2.55Sulfur, PPM 5800 8980 Operating conditions Reaction temperature, ° C.680 540 Product yields, wt % Dry Gas 31.78 5.1 Ethylene 17.48 2.3 LPG35.36 39.7 Propylene 19.72 15.9 Gasoline (C5-180° C.) 29.36 36.1 LCO —13.5

It is clearly evident from the Example-8 and Example-9 that the sum ofyields of ethylene and propylene is much superior in the presentinvention than that in the conventional process.

The embodiments of the present invention referred to in the abovedescription and examples are for illustration only and not construed tobe limitative. Other possible embodiments of the invention will beapparent to these skilled in the art from consideration of thespecification and practice of the invention disclosed herein. The exactscope and spirit of the invention are intended to be governed by thefollowing claims.

1. A FCC catalyst system for simultaneous cracking of lighter andheavier hydrocarbon feedstocks in multiple reactors to produce improvedyields of light olefins and liquid aromatics and the like, comprisingY-zeolite in rare earth ultra-stabilized form with bottom crackingcomponents consisting of peptized alumina, acidic silica alumina orgamma alumina, pentasil shape selective zeolites or a mixture thereof asthe active components.
 2. The catalyst system as claimed in claim 1,wherein the catalyst comprises of solid micro-spherical acidic materialswith average particle size of 60-80 microns and apparent bulk density of0.7 to 1.0 gm/cc.
 3. The catalyst system as claimed in claim 1, whereinthe active catalyst components are supported on relatively inactivematerials such as silica/alumina or silica-alumina compounds, includingkaolinites or with active matrix components like pseudobomite alumina.4. A process for preparing a catalyst system for simultaneous crackingof lighter and heavier hydrocarbon feedstocks in multiple reactors toproduce improved yields of light olefins and liquid aromatics and thelike, wherein Y-zeolite in rare earth ultra-stabilized form and a bottomcracking component selected from peptized alumina, acidic silica aluminaor gamma alumina, pentasil shape selective zeolites or a mixture thereofare mixed together or separately bound, supported on relatively inactivematerials and spray-dried to get micro-spheres, washed, rare earthexchanged and flash dried to produce the finished catalyst system. 5.The process as claimed in claim 4, wherein the active catalystcomponents as finished micro-spheres in separate particles arephysically blended in the desired composition.
 6. A multi-reactorfluidized bed catalytic cracking apparatus for the production of lightolefins and liquid aromatics and the like, through simultaneous crackingof lighter and heavier hydrocarbon feedstocks in separate reaction zonescomprising at least a first reaction zone in a first reactor, a secondreaction zone in a second reactor and a catalyst regenerator.
 7. Theapparatus as claimed in claim 6, wherein the first reactor beingconnected at the bottom with a distributor inlet for entry of preheatedlighter hydrocarbon feed/recycled feed along with process steam via aconduit, has an inlet for entry of hot regenerated catalyst through adistributor via a slide valve from the catalyst regenerator, aseparation device for separation of coke laden catalyst from the crackedproducts, a stripper means for stripping coked catalyst from the crackedproduct vapor, an outlet for the product vapor to reach to a mainfractionator via a plenum chamber; an outlet at the bottom forcirculation of partially coked catalyst to the bottom of the secondreactor through a slide valve; an outlet for removing coke laden spentcatalyst to the regenerator; the second reactor, preferably a riser,having an inlet for hot fresh heavy feedstock with dispersion steam nearthe bottom through a single or multiple feed nozzle, an inlet each forrecycle feed and dilution steam near the bottom at different elevationsof the riser and at the bottom for the regenerated catalyst throughslide valve stated above and for the lift/stabilization steam; atermination device with separator for the separation of spent catalystand product vapor mixture, a stripper means for stripping coke ladencatalyst from the cracked hydrocarbons, an outlet for the spent catalystto the regenerator, an outlet for the product vapor to the mainfractionator via a plenum chamber; the catalyst regenerator has an inletfor the source of coke laden spent catalyst distributed through adistributor, an inlet at the bottom for the source of air or an oxygencontaining gas, an outlet for the regenerated catalyst linked to thefirst reactor, a separation device for separating flue gas from theregenerated catalyst, an outlet for the flue gas and an outlet for theregenerated catalyst linked to the first reactor.
 8. The apparatus asclaimed in claim 6, wherein the catalyst regenerator is a single stageor multistage regenerator.
 9. The apparatus as claimed in claim 6,wherein the distributor is selected from manifold type, concentric ringtype, perforated plate type and the like.